The invention relates to a transparent, biaxially oriented polyester film with a base layer B which comprises at least 80% by weight of thermoplastic polyester, and with at least one intermediate layer Z, and with at least one outer layer A. The invention further relates to the use of the film and to a process for its production.
EP-A-0 878 297 describes a transparent, biaxially oriented polyester film with a base layer B, at least 80% by weight of which is composed of a thermoplastic polyester, and with at least one outer layer A which is composed of a mixture of polymers which contains at least 40% by weight of ethylene 2,6-naphthalate units (PEN) and up to 40% by weight of ethylene terephthalate units (PET) and/or up to 60% by weight of units derived from cycloaliphatic or aromatic diols and/or dicarboxylic acids.
If the outer layer A of the film of EP-A-0 878 297 contains high concentrations of ethylene 2,6-naphthalate units, the film has a tendency for delamination between the outer layer A and the base layer B. If, on the other hand, the outer layer A contains low concentrations of ethylene 2,6-naphthalate units, the thickness of this layer has to be raised in order to achieve the desired low oxygen permeation of not more than 80 cm3/(m2xc2x7barxc2x7d).
In a film in Example 8 of EP-A-0 878 297 the outer layer A uses pure polyethylene 2,6-naphthalate (corresponding to 100% by weight of ethylene 2,6-naphthalate units). In this case there is no significant adhesion between the outer layer A and the base layer B. The film is unsuitable for industrial use (e.g. as a composite film), since the bond releases even when subjected to a low level of mechanical stress, due to the low adhesion between the outer layer A and the base layer B of the polyester film.
In a film in Example 11 of EP-A-0 878 297, the outer layer A contains 60% by weight of ethylene 2,6-naphthalate units. In order to achieve the low oxygen permeation demanded, below 80 cm3/(m2xc2x7barxc2x7d), the thickness of the outer layer A has to be raised to 3 xcexcm, and this is economically disadvantageous (high capital expenditure and high material costs).
U.S. Pat. No. 5,795,528 describes a coextruded film laminate which has alternating layers of PEN and PET. Like the film of EP-A-0 878 297, this film has a tendency toward delamination between the individual layers of PEN and PET. There is no significant adhesion between these layers. A laminate of this type is therefore again unsuitable for industrial use.
It was an object of the present invention, therefore, to provide a transparent, biaxially oriented polyester film which overcomes the disadvantage of the prior art films and in particular has improved adhesion between the individual layers. It should be simple and cost-effective to produce, have good barrier properties, and pose no problems of disposal.
The object is achieved by means of a transparent, biaxially oriented polyester film with a base layer B which comprises at least 80% by weight of thermoplastic polyester, with at least one intermediate layer Z, and with at least one outer layer A, the characterizing features of which are regarded as being that
the outer layer A is composed of a polymer, of a mixture of polymers/copolymers, or of a copolymer, which contains at least 85% by weight of ethylene 2,6-naphthalate units and up to 15% by weight of ethylene terephthalate units, and/or up to 15% by weight of units derived from cycloaliphatic or aromatic diols and/or dicarboxylic acids;
the intermediate layer Z is composed of a mixture of polymers/copolymers, or of a copolymer, which contains at least 3% by weight of ethylene 2,6-naphthalate units, and up to 97% by weight of ethylene terephthalate units, and/or up to 97% by weight of units derived from cycloaliphatic or aromatic diols and/or dicarboxylic acids, and
the Tg2 value of the polyester film is above the Tg2 value of the base layer B but below the Tg2 value of the outer layer A.
The film of the invention has low oxygen permeation, below 85 cm3/(m2xc2x7barxc2x7d), and minimum adhesion (between the individual layers) greater than 0.5 N/25 mm.
The structure of the film of the invention has at least three layers, and is then composed of the outer layer A, of a base layer B, and of an intermediate layer Z located between the outer layer A and the base layer B.
Preference is given to a polyester film in which the polymers of the outer layer A contain at least 90% by weight of ethylene 2,6-naphthalate units and up to 10% by weight of ethylene terephthalate units. Among these, particular preference is in turn given to a polyester film in which the polymers of the outer layer A contain at least 92% by weight of ethylene 2,6-naphthalate units and up to 8% by weight of ethylene terephthalate units. However, the outer layer A may also be composed entirely of ethylene 2,6-naphthalate polymers.
Preference is also given to a polyester film in which the polymers of the intermediate layer Z contain at least 5% by weight of ethylene 2,6-naphthalate units and up to 95% by weight of ethylene terephthalate units. Among these, particular preference is in turn given to a polyester film in which the polymers of the intermediate layer Z contain at least 7% by weight of ethylene 2,6-naphthalate units and up to 93% by weight of ethylene terephthalate units.
Examples of suitable aliphatic diols are diethylene glycol, triethylene glycol, aliphatic glycols of the formula HOxe2x80x94(CH2)nxe2x80x94OH, where n is an integer from 3 to 6 (in particular 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol), or branched aliphatic glycols having up to 6 carbon atoms, and cycloaliphatic diols having one or more rings and if desired containing heteroatoms. Among the cycloaliphatic diols, mention may be made of cyclohexanediols (in particular 1,4-cyclohexanediol). Examples of other suitable aromatic diols are those of the formula HOxe2x80x94C6H4xe2x80x94Xxe2x80x94C6H4xe2x80x94OH where X is xe2x80x94CH2xe2x80x94, xe2x80x94C(CH3)2xe2x80x94, xe2x80x94C(CF3)2xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94SO2xe2x80x94. Besides these, bisphenols of the formula HOxe2x80x94C6H4xe2x80x94C6H4xe2x80x94OH are also very suitable.
Preferred aromatic dicarboxylic acids are benzenedicarboxylic acids, naphthalenedicarboxylic acids (for example naphthalene-1,4- or -1,6-dicarboxylic acid), biphenyl-x,xxe2x80x2-dicarboxylic acids (in particular biphenyl-4,4xe2x80x2-dicarboxylic acid), diphenylacetylene-x,xxe2x80x2-dicarboxylic acids (in particular diphenylacetylene-4,4xe2x80x2-dicarboxylic acid) or stilbene-x,xxe2x80x2-dicarboxylic acids. Among the cycloaliphatic dicarboxylic acids, mention may be made of cyclohexanedicarboxylic acids (in particular cyclohexane-1,4-dicarboxylic acid). Among the aliphatic dicarboxylic acids, the C3-C19-alkanedioic acids are particularly suitable, where the alkane moiety may be straight-chain or branched.
The base layer of the film is preferably composed of at least 90% by weight of the thermoplastic polyester. Polyesters suitable for this are those made from ethylene glycol and terephthalic acid (=polyethylene terephthalate, PET), from ethylene glycol and naphthalene-2,6-dicarboxylic acid (=polyethylene 2,6-naphthalate, PEN), from 1,4-bishydroxymethylcyclohexane and terephthalic acid (=poly-1,4-cyclohexanedimethylene terephthalate, PCDT), and also from ethylene glycol, naphthalene-2,6-dicarboxylic acid and biphenyl-4,4xe2x80x2-dicarboxylic acid (=polyethylene 2,6-naphthalate bibenzoate, PENBB). Particular preference is given to polyesters which are composed of at least 90 mol %, preferably at least 95 mol %, of ethylene glycol units and terephthalic acid units or of ethylene glycol units and naphthalene-2,6-dicarboxylic acid units. The remaining monomer units are derived from other diols and/or dicarboxylic acids. Examples of suitable diol comonomers are diethylene glycol, triethylene glycol, aliphatic glycols of the formula HOxe2x80x94(CH2)nxe2x80x94OH, where n is an integer from 3 to 6, branched aliphatic glycols having up to 6 carbon atoms, aromatic diols of the formula HOxe2x80x94C6H4xe2x80x94Xxe2x80x94C6H4xe2x80x94OH where X is xe2x80x94CH2xe2x80x94, xe2x80x94C(CH3)2xe2x80x94, xe2x80x94C(CF3)2xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94SO2xe2x80x94, or bisphenols of the formula HOxe2x80x94C6H4xe2x80x94C6H4xe2x80x94OH are employed.
The dicarboxylic acid comonomer units are preferably derived from benzene-dicarboxylic acids, naphthalenedicarboxylic acids, biphenyl-x,xxe2x80x2-dicarboxylic acids (in particular biphenyl-4,4xe2x80x2-dicarboxylic acid), cyclohexanedicarboxylic acids (in particular cyclohexane-1,4-dicarboxylic acid), diphenylacetylene-x,xxe2x80x2-dicarboxylic acids (in particular diphenylacetylene-4,4xe2x80x2-dicarboxylic acid), stilbene-x,xxe2x80x2-dicarboxylic acid or C1-C16-alkanedicarboxylic acids, where the alkane moiety may be straight-chain or branched.
The polyesters may be prepared by the transesterification process. The starting materials for this are dicarboxylic esters and diols, which are reacted using the customary transesterification catalysts, such as salts of zinc, of calcium, of lithium and of manganese. The intermediates are then polycondensed in the presence of widely used polycondensation catalysts, such as antimony trioxide or titanium salts. The preparation may be carried out just as successfully by the direct esterification process in the presence of polycondensation catalysts, starting directly from the dicarboxylic acids and the diols.
The polymers/copolymers for the outer layer A and for the intermediate layer Z may be prepared in three different ways:
a) In copolycondensation, terephthalic acid and naphthalene-2,6-dicarboxylic acid are placed in a reactor together with ethylene glycol, and polycondensed to give a polyester, using the customary catalysts and stabilizers. The terephthalate and naphthalate units are then randomly distributed in the polyester.
b) Polyethylene terephthalate (PET) and polyethylene 2,6-naphthalate (PEN), in the desired ratio, are melted together and mixed, either in a reactor or preferably in a melt kneader (twin-screw kneader) or in an extruder. Immediately after the melting, transesterification reactions between the polyesters begin. Initially, block copolymers are obtained, but as reaction time increasesxe2x80x94depending on the temperature and mixing action of the agitatorxe2x80x94the blocks become smaller, and long reaction times give a random copolymer. However, it is not necessary and also not always advantageous to wait until a random distribution has been achieved, since the desired properties are also obtained with a block copolymer. The resultant copolymer is then extruded from a die and granulated.
c) PET and PEN are mixed as granules in the desired ratio, and the mixture is fed to the extruder for the outer layer A. Here, the transesterification to give the copolymer takes place directly during the production of the film. This process has the advantage of being very cost-effective, and generally gives block copolymers, the block length being dependent on the extrusion temperature, the mixing action of the extruder and the residence time in the melt.
In a preferred embodiment of the invention, from 0.1 to 20% by weight of the polymers of the base layer B are identical with those of the outer layer A and with those of the intermediate layer Z. These are either directly admixed with the base layer B during extrusion or are in any case present in the film due to addition of regrind. The proportion of these copolymers in the base layer is selected in such a way that the base layer has crystalline character.
In another advantageous embodiment, the film encompasses, on the side facing away from the outer layer A, another outer layer C of polyethylene terephthalate, and this layer comprises pigments.
The film of the invention has a high oxygen barrier and high adhesion between its individual layers. If, in contrast, the polymers used for the outer layer A contain less than 85% of ethylene 2,6-naphthalate units and more than 15% by weight of ethylene terephthalate units, although the film then has somewhat less permeability to oxygen than a standard polyester film (composed of 100% by weight of polyethylene terephthalate), its permeability is still much too high.
If the copolymers used for the intermediate layer Z contain less than 3% by weight of ethylene 2,6-naphthalate units and more than 97% by weight of ethylene terephthalate units, the adhesion between the outer layer A and the intermediate layer Z becomes inadequate. When subjected to mechanical stress the film tends toward delamination, which is undesirable and makes the film unusable.
A difference from the prior art is that in films of the invention moreover the glass transition temperature Tg of the (co)polymer or of the (co)polymers of the outer layer A is higher than the glass transition temperature Tg of the polymers for the intermediate layer Z and for the base layer B. The glass transition temperature Tg of the (co)polymers used for the outer layer A is preferably in the range from 90 to 120xc2x0 C. In the DSC (differential scanning calorimetry) determination of the glass transition temperatures Tg, the transitions of the layers cannot be differentiated.
Glass transitions which are determined on biaxially oriented, heat-set films in the first heating procedure (termed Tg1 below) are, due to crystallinity and also to molecular stresses in the amorphous fraction of the specimens, relatively small in size, distributed over a wide temperature range, and shifted to higher temperatures. Because of orientation effects in particular, they are not suitable for characterizing a polymer. The resolution of DSC analyzers is often insufficient to detect the glass transitions in the first heating procedure (Tg1) of the individual layers of the film of the invention, the transitions being xe2x80x9cblurredxe2x80x9d and small, due to orientation and crystallinity.
If the specimens are melted and then rapidly cooled again to below their glass transition temperature (quenched), the orientation effects are eliminated. On renewed heating, glass transitions (designated Tg here) are then measured which have a greater intensity and are characteristic of the respective polymers. However, even here it is not possible to differentiate the glass transitions of the individual layers, since the layers mix on melting and the polyesters present therein enter into transesterification reactions with one another. It is fully sufficient, however, to compare the Tg2 of the entire coextruded films with the Tg2 of the polymer used for the base layer B. In known films the Tg2 value of the base layer is higher than that of the coextruded film, whereas the Tg2 value of the outer layer is lower than that of the base layer and also than that of the coextruded film. Exactly the opposite of this applies for the film of the invention. Here, the Tg2 value of the coextruded film is higher than that of the base layer B but below the Tg2 value of the outer layer A.
The base layer B, the intermediate layer Z, and the outer layer(s) may also comprise customary additives, such as stabilizers and antiblocking agents. They are expediently added to the polymer or to the polymer mixture even before melting takes place. Examples of stabilizers are phosphorus compounds, such as phosphoric acid and phosphoric esters. Typical antiblocking agents (also termed pigments in this context) are inorganic and/or organic particles, for example calcium carbonate, amorphous silica, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, LiF, the calcium, barium, zinc and manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, kaolin, crosslinked polystyrene particles and crosslinked acrylate particles.
The additives selected may also be mixtures of two or more different antiblocking agents or mixtures of antiblocking agents of the same makeup but of different particle size. The particles may be added to the individual layers in the customary concentrations, e.g. as glycolic dispersion during polycondensation or via masterbatches during extrusion. Pigment concentrations of from 0.0001 to 5% by weight have proven particularly suitable. A detailed description of the antiblocking agents is found, for example, in EP-A-0 602 964.
The film may be coated and/or corona- or flame-pretreated to establish other desired properties. Typical coatings are layers which promote adhesion, are antistatic, improve slip, or have release action. These additional layers may be applied to the film by in-line coating using aqueous dispersions, before transverse orientation. The film is also particularly suitable for metallizing or coating with ceramic substances (SiOx, Al2O3). Particularly good oxygen barrier values are achieved if the outer layer A is metallized or ceramic-coated.
The polyester film of the invention preferably also comprises a second outer layer C. The structure, thickness, and makeup of the second outer layer C may be selected without reference to the outer layer A already present, and the second outer layer C may also comprise the abovementioned polymers or polymer mixtures, but these do not have to be identical with the chemical makeup of outer layer A. The second outer layer C may also comprise other commonly used outer layer polymers.
Between the base layer B and the outer layer A, there is the intermediate layer Z. The thickness of the intermediate layer is generally above 0.1 xcexcm and is preferably in the range from 0.2 to 20 xcexcm, particularly preferably in the range from 0.3 to 10 xcexcm.
The thickness of the outer layer(s) is generally above 0.3 xcexcm, preferably in the range from 0.4 to 5 xcexcm, and particularly preferably in the range from 0.5 to 4 xcexcm, and the thicknesses of the outer layers may be identical or different.
The total thickness of the polyester film of the invention may vary within wide limits and depends on the application envisaged. It is preferably from 4 to 100 xcexcm, in particular from 5 to 50 xcexcm, with preference from 6 to 30 xcexcm, the proportion of the total thickness made up by the base layer preferably being from about 40 to 90%.
The present invention also provides a process for producing this film. It encompasses
a) producing a film having two or more layers from a base layer B and outer layer(s) A and, where appropriate, C, by coextrusion;
b) biaxially stretching the film, and
c) heat-setting the stretched film.
To produce the outer layer A, it is expedient to feed granules of polyethylene terephthalate and polyethylene 2,6-naphthalate directly to the extruder in the desired mixing ratio. At about 300xc2x0 C., the two materials can be melted and can be extruded. Under these conditions, transesterification reactions can occur in the extruder and during these copolymers are formed from the respective homopolymers.
The polymers for the base layer B are expediently fed in via another extruder. Any foreign bodies or contamination which may be present can be filtered off from the polymer melt before extrusion. The melts are then extruded through a coextrusion die to give flat melt films and are layered one upon the other. The composite film is then drawn off and solidified with the aid of a chill roll and other rolls if desired.
The biaxial stretching is generally carried out sequentially, stretching first longitudinally (i.e. in the machine direction) and then transversely (i.e. perpendicularly to the machine direction). This leads to orientation of the molecular chains within the polyester. The longitudinal stretching can be carried out with the aid of two rollers rotating at different rates corresponding to the desired stretching ratio. For the transverse stretching, use is generally made of an appropriate tenter frame.
The temperature at which the orientation procedure is carried out can vary over a relatively wide range and depends on the properties desired in the film. In general, the longitudinal stretching is carried out at from 80 to 130xc2x0 C., and the transverse stretching at from 90 to 150xc2x0 C. The longitudinal stretching ratio is generally in the range from 2.5:1 to 6:1, preferably from 3:1 to 5.5:1. The transverse stretching ratio is generally in the range from 3.0:1 to 5.0:1, preferably from 3.5:1 to 4.5:1.
During the subsequent heat-setting, the film is held for from 0.1 to 10 s at a temperature of from 150 to 250xc2x0 C. The film is then wound up in a conventional manner.
A great advantage of this process is that it is possible to feed the extruder with granules, which do not block the machine.
A further advantage is that the production costs of the film of the invention are only insignificantly greater than those of a film made from standard polyester raw materials. The other properties of the film of the invention which are relevant to its processing and its use remain essentially unchanged or have even been improved. It has also been ensured that cut material arising directly in the plant during film production can be used again in the form of regrind for film production in amounts of up to 60% by weight, preferably from 10 to 50% by weight, based in each case on the total weight of the film, without any significant resultant adverse effect on the physical properties of the film produced with incorporation of regrind.
The film of the invention has excellent suitability for packaging food or other consumable items. It has excellent barrier properties, in particular with respect to oxygen. It has been assured that the individual layers of the film remain adhering to one another when the film is processed, e.g. to give film laminates, and do not delaminate.
It is also possible to improve the gloss and the haze of the film, compared with prior art films. It has been ensured that regrind can be reintroduced to the extrusion process during production of the film at a concentration of up to 60% by weight, based on the total weight of the film, without any significant resultant adverse effect on the physical properties of the film.
The very good handling properties of the film and its excellent processing properties make it particularly suitable for processing on high-speed machinery.
The table below (Table 1) gives the most important film properties of the invention again at a glance for quick reference.
Test Methods
The following methods were utilized to characterize the raw materials and the films:
Oxygen Permeability
The oxygen barrier test took place using a Mocon Modern Controls (USA) OX-TRAN 2/20, as in DIN 53 380, Part 3.
SV (Standard Viscosity)
The standard viscosity SV (DCA) is measured by analogy with DIN 53726, at 25xc2x0 C. in dichloroacetic acid. The intrinsic viscosity (IV) is calculated from the standard viscosity as follows
IV=[xcex7]=6.907xc2x710xe2x88x924SV (DCA)+0.063096 [dl/g].
Coefficient of Friction
The coefficient of friction was determined to DIN 53 375. The coefficient of sliding friction was measured 14 days after production.
Surface Tension
Surface tension was determined using what is known as the ink method (DIN 53 364).
Haze
The haze of the film was measured to ASTM-D1003-52. The Hxc3x6lz haze measurement was determined by analogy with ASTM-D1003-52, but, in order to utilize the ideal measurement range, measurements were taken on four pieces of film laid one on top of the other, and a 1xc2x0 slit diaphragm was used instead of a 4xc2x0 pinhole.
Gloss
Gloss was determined to DIN 67 530. The reflectance was measured, this being a characteristic optical value for a film surface. Based on the standards ASTM-D523-78 and ISO 2813, the angle of incidence was set at 20xc2x0 or 60xc2x0. A beam of light at the set angle of incidence hits the flat test surface and is reflected and/or scattered thereby. A proportional electrical variable is displayed representing light rays hitting the photoelectric detector. The value measured is dimensionless and must be stated together with the angle of incidence.
The glass transition temperatures Tg1 and Tg2 were determined with the aid of DSC (differential scanning calorimetry) on film specimens. A DuPont DSC 1090 was used. The heating rate was 20 K/min, and the specimen weight was about 12 mg. The glass transition Tg1 was determined in the first heating procedure. Many of the specimens showed an enthalpy relaxation (a peak) at the beginning of the step-like glass transition. The temperature taken as Tg1 was that at which the step-like change in heat capacityxe2x80x94ignoring the enthalpy relaxation peakxe2x80x94achieved half of its height in the first heating procedure. In all cases, there was only a single glass transition stage in the thermogram in the first heating procedure. It is possible that the enthalpy relaxation peaks obscured the fine structure of the transition, or that the resolution of the device was not adequate to separate the small, xe2x80x9cblurredxe2x80x9d transitions of oriented, crystalline specimens. In order to eliminate their heat history the specimens were held at 300xc2x0 C. for 5 minutes after the heating procedure, and then quenched with liquid nitrogen. The temperature for the glass transition Tg2 was taken as the temperature at which the transition reached half of its height in the thermogram for the second heating procedure.
Adhesion Between the Layers
Prior to adhesive bonding, the specimen of film (300 mm longxc3x97180 mm wide) of the present invention is placed on a smooth piece of card (200 mm longxc3x97180 mm wide; about 400 g/m2, bleached, outer laps coated). The overlapping margins of the film are folded back onto the reverse side and secured with adhesive tape.
For adhesive bonding of the film according to the present invention, use is made of a standard polyester film of 12 xcexcm thickness (e.g. Melinex 800), and a doctor device and doctor bar No. 3 from Erichsen, applying about 1.5 ml of adhesive (Novacote NC 275+CA 12; mixing ratio: 4/1+7 parts of ethyl acetate) to the outer layer A of the film of the present invention. After aerating to remove the solvent, the standard polyester film is laminated to outer layer A of the film of the present invention using a metal roller (width 200 mm, diameter 90 mm, weight 10 kg, to DIN EN 20 535). The lamination parameters are:
A 25xc2x11 mm strip cutter is used to take specimens about 100 mm in length. About 50 mm of composite is needed here, and 50 mm of unbonded separate laps for securing/clamping the test specimen. The test specimens are secured to a sheet metal support by means of double-sided adhesive tape, by way of the entire surface of the reverse side of the film of the present invention (base layer B or outer layer C). The sheet with the composite adhesively bonded thereto is clamped into the lower clamping jaw of the tensile test machine. The clamp separation is 100 mm. The unlaminated end of the standard polyester film is clamped into the upper clamping jaw of the tensile test machine (e.g. Instron, Zwick) so that the resultant peel angle is 180xc2x0. The average peel force in N/25 mm is given, rounded to one decimal place.
The peel force test result is equivalent to the minimum adhesion between the layers, since the adhesion between the adhesive and the standard film is markedly greater. A UV lamp, for example, can be used to demonstrate the release of the outer layer A from the base layer B of the film of the present invention. The UV light has a blueish appearance if copolymer of PEN and PET is present on the adhesive and this layer is irradiated using a UV lamp.